KR100339776B1 - Antimicrobial materials, antimicrobial resin compositions, antimicrobial synthetic fibers, paper with antimicrobial properties, antimicrobial paints, cosmetics and methods for producing antimicrobial materials - Google Patents

Abstract

Provided are antimicrobial agents having high antimicrobial properties and sustainability and high safety and resin compositions containing them, resin moldings, antimicrobial fibers, paper having antimicrobial properties, antimicrobial paints, topical antimicrobials, cosmetics and antimicrobial materials.

In the antimicrobial material of the present invention, a metal having an antimicrobial activity is bonded to an N-long chain acylamino acid directly attached to the surface of an inorganic particle or a synthetic resin particle by a hydrophilic organic material or directly. The method for producing an antimicrobial agent of the present invention includes a step of bringing the particles into contact with an N-long-chain acylamino acid ion-containing aqueous solution, and thereafter a step of contacting the particles with a metal-containing aqueous solution having an antibacterial action.

Description

Antimicrobial materials, antimicrobial resin compositions, antimicrobial synthetic fibers, paper with antimicrobial properties, antimicrobial paints, cosmetics and methods for producing antimicrobial materials

[Industrial use]

The present invention relates to a novel antimicrobial material having an antimicrobial effect against various bacteria and fungi, and furthermore, to the antimicrobial resin composition containing the same, antimicrobial resin molding, antimicrobial fiber, paper having antimicrobial properties, antimicrobial paints, cosmetics and antibacterial materials It relates to a manufacturing method.

[Prior art]

Conventionally, it is known that silver and copper have a bactericidal action, for example, silver is widely used as a disinfectant in the form of an aqueous solution such as silver nitrate (Ag ⁺ ).

It is also known to adsorb silver or a compound thereof to an adsorbent such as activated carbon, alumina, silica gel, zeolite and the like for sterilization purposes.

As mentioned above, there exist some which are shown by Unexamined-Japanese-Patent No. 62-241939 and Unexamined-Japanese-Patent No. 62-238900, These are the polyolefin resin moldings and paper containing the zeolite which hold | maintains the metal which has a bactericidal effect in ion state. .

Also as shown in Japanese Patent No. 62-70221 points formula M ₂ O and Al ₂ O ₃ and SiO ₂ (wherein M is is the like), an amorphous (amorphous) silica-alumina having an antibacterial and / or bactericidal action indicated by .

Conventionally, the attachment of aquatic organisms to water (including seawater) contact parts in marine aquatic structures (e.g., offshore structures such as petroleum excavation leagues, docks, buoys, dike, power plant waterways, buoys, etc.). Antifouling paints are used to prevent this.

And antifouling paints are formulated with antifouling agents effective for preventing adhesion of aquatic organisms (for example, moss insects, oblivion, bivalve shells, sea squirts, seaweeds, etc.).

As the antifouling agent component, various compounds are used. For example, a copper compound such as a high molecular weight organic organocompound compound in which a triphenyl tin compound or a trialkyl tin compound is bonded to an acrylic resin or an alkyd resin, copper nitrous oxide and rhodan copper, and zinc dimethyl Organic sulfur compounds, such as thiocarbanate and tetramethyl thiurem disulfamide, are used.

In recent years, especially after the completion of the construction of the building, the mold and the wall, windows and papers significantly reverberate, and the pigments, which are metabolites, are often stained. This is attributable to the improvement of the airtightness of the building by the spread of alumina chassis, the improvement of living conditions in the house by the spread of air conditioning and heating, the use of humidifiers, and the like. The improved conditions also apply to microorganisms such as molds and bacteria. It gives a suitable growth environment.

For this reason, it is possible to grow microorganisms throughout the year.

Molds on wallpaper or window coverings are penicillium, aspergillus, cladporium, and the like. Colored spots occurring on wallpaper are often caused by bacteria of the genus Aspergillus. During the process of floating paper, especially wallpaper and window paper, starch, carboxymethylcellulose, and the like are added to the pulp as a sizing agent, which becomes a nutrient source for fungi and microorganisms of microorganisms. It gives the right development environment.

In the case of window papers, for example, the occurrence of molds occurs 4 to 5 months after application of window papers, and half a year to 1 year later, and colored spots occur.

In addition, when the occurrence of mold is remarkable, it is necessary to reapply windows and windows, which is a big problem economically and effortfully.

In addition, there are many cosmetic products that have been conventionally used by methods such as coating and spreading on the skin.

And many additives (preparation) are used for cosmetics, For example, surfactant, a pigment, a moisturizer, a fragrance | flavor, antioxidant, an antiseptic | microbial agent, an antiseptic agent, an ultraviolet reflector, etc. are mentioned.

[Problems that the invention tries to solve]

Silver nitrate conventionally used is limited to the form of aqueous solution, and since it is a solution form, handling is inconvenient, and there existed a fault that a use is limited.

What is displayed in Japanese Patent Laid-Open No. 62-241939, Japanese Patent Laid-Open No. 62-238900, and Japanese Patent Laid-Open No. 62-70221 has an effect as an antibacterial action and a bactericidal action, Since the metal having the oxidized and discolored by light (especially ultraviolet rays), the whole substance also had a problem of discoloring.

Furthermore, the metal having the bactericidal properties being used is easily ionized, and therefore, when contacted with liquids or the like, it is easy to leak and there is a problem in stability.

In the conventional paints, the antifouling effect is not necessarily satisfied, and is further limited to specific ones as preservatives which can be used from problems such as seawater pollution, but is still not satisfactory in terms of safety.

In addition, although various methods have been considered to impart antimicrobial action to paper, the present invention has not been sufficiently satisfied in terms of antibacterial action and safety.

In addition, there is no conventional cosmetic additive that satisfies the deodorizing action sufficiently, satisfies the antibacterial action sufficiently, is stable and has high biosafety, and can be easily incorporated into cosmetics.

[Means for solving the problem]

Here, the object of the present invention is to solve the problems of the prior art, and has a high antimicrobial activity and its sustainability, and at the same time high safety antimicrobial agent, and a resin composition, resin molding, antimicrobial fiber, antimicrobial properties containing the same It provides a paper, antimicrobial paint, topical antibacterial material, cosmetics and a method for producing the antimicrobial material.

Achieving the above object is an antibacterial material in which a metal having an antimicrobial activity is bonded to an N-long chain acyl amino acid attached to a surface of an inorganic particle by a hydrophilic organic substance.

In other words, a metal having an antimicrobial action on the surface of the inorganic particle is an antimicrobial agent to which an N-long chain acylamino acid salt is attached by a hydrophilic organic material.

In addition, the above object is an antibacterial material in which a metal having an antimicrobial activity is bonded to an N-long chain acylamino acid attached to the surface of synthetic resin particles or inorganic particles.

In other words, the N-long-chain acylamino acid salt of the metal which has an antimicrobial effect adheres to the surface of synthetic resin particle.

And, it is preferable that the acyl group of the said N-long-chain acylamino acid salt is any of a stearoyl group, a lauroyl group, a myristoyl group, and a palmitoyl group.

Further, the metal is preferably any one selected from the group consisting of silver, copper, lead, zinc, tin and bismuth. In addition, two or more N-long-chain acylamino acid salts to which the other metal having an antimicrobial action is attached are attached to the particles.

In addition, the above object is achieved by the first antimicrobial inorganic particles in which a first metal having an antimicrobial action is bonded to an N-long chain acylamino acid salt attached to a surface of the inorganic particle by a hydrophilic organic substance, and an inorganic particle. An antimicrobial agent composed of a mixture of N-long-chain acylamino acid salts attached to the surface of a hydrophilic organic substance by a second antimicrobial inorganic particle in which a second metal having an antimicrobial action different from the first inorganic particle is bound to to be.

In other words, the first antimicrobial inorganic particles to which the N-long chain acylamino acid salt of a metal having a first antimicrobial action is attached to a surface of the inorganic particle by a hydrophilic organic material, and the first inorganic particle have antimicrobial action. A second N-long chain acylamino acid salt having a different metal is an antibacterial material comprising a mixture with second antimicrobial inorganic particles attached to a surface by a hydrophilic organic material.

In addition, the above object is achieved by attaching N-long chain acylamino acid attached to the surface of synthetic resin particles or inorganic particles to first antimicrobial synthetic resin particles having a first metal having an antimicrobial action, and to the surface of synthetic resin particles. An N-long chain acylamino acid is an antimicrobial material comprising a mixture of a second antimicrobial synthetic resin in which a second metal having a different antimicrobial effect is bonded to the first synthetic resin particle.

In other words, the first antimicrobial particles to which the N-long chain acylamino acid salt of the metal having the first antimicrobial action adheres to the surface of the synthetic resin particle or the inorganic particle, and the metal having the antimicrobial action with the first antimicrobial particle Another 2nd N-long-chain acylamino acid salt is an antimicrobial material which consists of a mixture with the 2nd antimicrobial particle adhering to the surface of a synthetic resin particle or an inorganic particle. And it is preferable that the said inorganic particle has a cation surface.

Moreover, what achieves the said objective is an antimicrobial resin composition containing said antimicrobial material.

Moreover, what achieves the said objective is an antimicrobial resin composition in which at least one part of surface is formed by said antimicrobial resin composition.

Moreover, it is the antimicrobial fiber containing said antimicrobial material to achieve the said objective.

Moreover, it is the paper which has the antimicrobial property containing the said antimicrobial material, or which the antimicrobial material adhered to the surface in order to achieve the said objective.

Moreover, it is an antimicrobial paint containing said antimicrobial material to achieve the said objective.

Moreover, it is the cosmetic containing the said antibacterial material to achieve the said objective.

The above object is also achieved by a step of attaching a hydrophilic organic material to the surface of the inorganic particles, a step of contacting the particles having the hydrophilic organic material adhered to the surface with an N-long-chain acylamino acid ion-containing aqueous solution, and after the step And it is a method of producing an antimicrobial material having a step of contacting the particles with a metal-containing aqueous solution having an antibacterial action.

In addition, the above object is achieved by an antibacterial process comprising contacting a synthetic resin particle or an inorganic particle with an N-long chain acylamino acid ion-containing aqueous solution, and thereafter contacting the particle with a metal ion-containing aqueous solution having an antimicrobial effect. It is a method of manufacturing ash.

Furthermore, the step of contacting the particles with a metal ion-containing aqueous solution having an antimicrobial action comprises contacting the particles with an aqueous solution containing two or more other metal ions having an antimicrobial action, or a first antimicrobial action. It is preferable to carry out by making it contact with a metal ion containing aqueous solution, and then making it contact with the metal ion which has the antibacterial effect, and the metal ion containing aqueous solution which has another 2nd antibacterial effect.

Here, the antimicrobial material of this invention is demonstrated.

The 1st antimicrobial material of this invention has the hydrophilic organic material layer which adhered to the surface of an inorganic particle, and the N-long-chain acylamino acid salt of the metal which has the antibacterial effect which adhered to the surface of this hydrophilic organic material layer.

More specifically, the antimicrobial agent has a hydrophilic organic material layer attached to the surface of the inorganic particles and an N-long chain acylamino acid salt attached to the surface of the hydrophilic organic material layer, and the N-long chain acylamino acid has an antibacterial effect. N-long chain acylamino acid salt combined with a metal having

More preferably, the antimicrobial material has a hydrophilic organic material attached to the surface of the inorganic particles first, and then an N-long chain acylamino acid adheres to the surface of the hydrophilic organic material layer, and after N-long chain acylamino acid is attached. The N-long-chain acylamino acid antimicrobial metal salt formed on the surface of an inorganic particle adheres by combining with the metal which has antibacterial effect, and N- long-chain acylamino acid.

That is, in this antimicrobial agonist, the N-long-chain acylamino acid water insoluble salt of the metal which has the antibacterial effect formed in the surface of an inorganic particle adheres to the surface of an inorganic particle by a hydrophilic organic substance.

In the antimicrobial material of the present invention, the inorganic particles make it easy to control the particle size of the antimicrobial material to be formed, and can produce an antimicrobial material having a particle size according to various uses.

In addition, the inorganic particles can prepare an antibacterial material having a high molecular antimicrobial activity and easy surface modification and surface modification.

Further, by using inorganic particles, the particle size and surface modification as described above can be performed, so that the formed antimicrobial material can be easily added to resins, fibers, paints and the like.

That is, dispersibility may not be enough only with N-long-chain acylamino acid antimicrobial metal salt, and dispersibility is improving.

As the inorganic particles, their stability, dispersibility, particle shape, uniformity of particle diameters and fine particles are obtained, and therefore ceramic particles, fine titanium powder (for example, fine titanium oxide powder) and fine calcium carbonate powder are preferable. As the ceramic particles, silica particles, alumina particles, zirconia particles, zeolite particles, silica-alumina particles and the like are suitably used. Especially preferred are silica particles.

And as a particle size of particle | grains, although it changes with a use to use, it is generally about 0.01 micrometer-1 mm, Preferably it is about 0.1 micrometer-10 micrometers.

Specifically, for example, in the case of the purpose of spreading to growth sites such as molds, the particles can be used even if they are somewhat large, and specifically, about 1 mm or less.

And in the case where the antimicrobial material of the present invention is mixed in the resin, in order not to alienate the transparency of the resin to be mixed, it is preferably 1 to 0.01 μm.

Moreover, also when mixing the antimicrobial material of this invention in a foam, about 1 micrometer or less, More preferably, it is 1-0.01 micrometer. Moreover, also when disperse | distributing in paper, about 1 micrometer or less, More preferably, it is 1-0.01 micrometer.

Moreover, also when disperse | distributing in paint, it is about 1 micrometer or less, More preferably, it is 1-0.01 micrometer.

The adhesion amount of N-long chain acylamino acid salt to particle | grains increases, so that the level to which antimicrobial property is calculated | required increases. In general, the ratio of the particles and the N-long-chain acylamino acid salt is preferably about 1000: 1 to 10: 1 by weight.

The hydrophilic organic material is for attaching the N-long chain acylamino acid to the surface of the inorganic particles, and the hydrophilic organic material has hydrophilicity for the affinity of the inorganic particles and organic nature for the affinity with the N-long chain acylamino acid.

More preferably, in order to make N-long-chain acyl anoic acid adhesion more certain, it is preferable that a hydrophilic organic substance has adhesiveness and film formation property.

Such hydrophilic organic substances include PVA (polyvinyl alcohol), modified PVA (e.g., carboxy modified PVA, sulfonic acid modified PVA, acrylamide modified PVA, carion group modified PVA, long chain alkyl group modified PVA), PVP (poly Vinylpyrrolidone), vinylpyrrolidone-vinyl acetate copolymer, cellulose materials such as carboxymethyl cellulose, methyl cellulose, oxypropyl cellulose, oxyethyl cellulose and the like.

Especially PVA and modified PVA are suitable.

And the N-long-chain acylamino acid salt which the metal which has antimicrobial effect couple | bonded is attached to the antimicrobial material of this invention.

As a metal which has an antimicrobial effect used for formation of the N-long-chain acylamino acid salt used for this invention, it is suitable to select from silver, copper, lead, zinc, tin, bismuth, etc.

And among these metals, silver or copper are particularly suitable in terms of antibacterial activity and safety.

The N-long chain acylamino acid used for formation of the N-long chain acylamino acid salt used for this invention is an amino acid which has a long chain acyl group (fatty acid residue) on N.

As the long-chain acyl group, a higher fatty acid residue is preferable, and for example, decanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oleoyl group and the like are preferable. Moreover, as an acyl group, it is not limited to a single thing, You may use the some kind of said acyl group.

As the amino acid part, any of monoamino monocarboxylic acid, monoamino dicarboxylic acid, and diamino monocarboxylic acid may be used. As the antimicrobial material of the present invention, when having high antimicrobiality, it is preferable to use monoaminodicarboxylic acid, and since this monoaminodicarboxylic acid has two carboxyl groups, metals having antibacterial action are likely to bind easily. It can be said that antibacterial effect is strong as a whole.

As a general use of antimicrobial materials, salts in which a metal having one antimicrobial activity is bound to an amino acid have sufficient antimicrobial activity.

Specific examples of the amino acids include glycine, alanine, baltin, leucine, phenylalanine, tyrosine, threonine, tripropane, methionine, and the like. As monoaminodicarboxylic acids, aspartic acid and glutamic acid are used as lysine, and diamino monocarboxylic acid. Arginine, histidine. And as N-long-chain acylamino acid, it is not limited to 1 type, You may use many types of things.

Therefore, as a preferable specific example of N-long-chain acylamino acid salt contained in the antimicrobial agent of this invention, N-stearoyl glutamic acid, N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-stearoyl aspartic acid Silver, N-lauroyl aspartic acid silver, N-myristoyl aspartic acid silver, N-stearoyl glutamate copper, N-lauroyl glutamate copper, N-myristoyl glutamate copper, N-stearoyl aspartic acid copper, N-lauroyl aspartic acid copper, N-myristoyl aspartic acid copper, N-stearoyl valine, N-lauroyl valine, N-myristoyl valine, N-stearoyl valine copper, N- Lauroyl valine copper, N-myristoyl valine copper, N-stearoyl phenyl alanine, N-lauroyl phenyl alanine, N- myristoyl phenyl alanine, N-stearoyl phenyl alanine copper, N-lauroyl phenyl alanine copper, N-myristoyl phen Ni-alanine copper, N-stearoyl arginine, N-lauroyl arginine, N-myristoyl arginine, N-stearoyl arginine copper, N-lauroyl arginine copper, N-myristoyl arginine Copper, N-stearoyl glutamate, N-lauroyl glutamate, zinc N-myristoyl glutamate, zinc N-stearoyl asparticate, zinc N-lauroyl asparticate, zinc zinc N-myristoyl aspartate, N-stearoyl glutamate bismuth, N-lauroyl glutamate bismuth, N-myristoyl glutamate bismuth, N-stearoyl aspartic acid bismuth, N-lauroyl aspartic acid bismuth, N-myristoyl aspartic acid bismuth, N- Stearoyl valine zinc, N-lauroyl valine zinc, N-myristoyl valine zinc, N-stearoyl valine zinc, N-lauroyl valine zinc, N-myristoyl valine bismuth, N-stearo Phenyl alanine Lead, N-lauroyl phenyl alanine zinc, N-myristoyl phenyl alanine zinc, N-stearoyl phenyl alanine bismuth, N-lauroyl phenyl alanine bismuth, N- myristoyl phenyl alanine bismuth, N-stea Royl Arginine Zinc, N-Lauroyl Arginine Zinc, N-Lauroyl Arginine Zinc, N-myristoyl Arginine Zinc, N-Stearoyl Arginine Bismuth, N-Lauroyl Arginine Bismuth, N-myristoyl Arginine bismuth, lead N-stearoyl glutamate, lead N-lauroyl glutamate, lead N-myristoyl glutamate, lead N-stearoyl aspartic acid, lead N-lauroyl aspartic acid, lead N-myristoyl aspartic acid , N-stearoyl glutamate tin, N-lauroyl glutamate tin, N-myristoyl glutamate tin, N-stearoyl aspartic acid tin, N-lauroyl aspartic acid tin, N-myristoyl aspartic acid tin, N Stea Yl valine tin, N-lauroyl valine tin, N-myritovyl valine tin, N-stearoyl phenyl alanine tin, N-lauroyl phenyl alanine tin, N-myristoyl phenyl alanine tin, N-stea Royl arginine tin, N-lauroyl arginine tin, and N-myristoyl arginine stock.

The N-long-chain acylamino acid salt is poorly soluble in water and various organic solvents.

In this antimicrobial agonist, the attached N-acylamino acid salt is a salt in which at least one antimicrobial metal is bound to each molecule, and thus has extremely high antimicrobial activity. Moreover, since it is an amino acid that forms a basic skeleton, it is extremely low in toxicity and can be safely used in various applications.

Furthermore, in the antibacterial material of the present invention, since the attached N-long-chain acylamino acid salt is in a stable state of (water) insolubility, only a metal forming a salt is difficult to flow out, and it is safe, and a wide range of resins such as food products It can be mixed in packaging materials such as moldings, films and paper.

Furthermore, it is preferable that two or more types of N-long-chain acylamino acid salts to which the other metal which has an antimicrobial effect couple | bonded adhere to the surface of an inorganic particle.

That is, it is preferable that two or more types of N-long-chain acylamino acid salts adhere to a particle | grain, and these N- long-chain acyl amino acid salts couple | bonded with the other metal which has antibacterial property. Since the antimicrobial material contains two or more antimicrobial metals in a salt state, the antimicrobial material has a broader antimicrobial spectrum than that of only one antimicrobial metal, and the antimicrobial activity is higher and more fungi It exerts antibacterial action. Moreover, two or more types of N-long-chain acylamino acid salts are salts of the metal which has antibacterial effect, and N-long-chain acylamino acid, At least a metal differs, and N-long-chain acylamino acid may be same or different.

In view of antibacterial activity and safety, it is preferable to use silver or copper as an essential metal, and to use at least one selected from other metals (silver, copper, lead, zinc, tin, bismuth, and the like). Moreover, as a more preferable combination, silver or copper is made into an essential metal, and 2 or more types are selected and used from another metal (silver, copper, lead, zinc, tin, bismuth, etc.).

Specific examples of preferred combinations include silver and copper, silver and zinc, silver and lead, copper and zinc, silver and copper and zinc, silver and copper and lead, silver and copper and bismuth, copper and zinc and lead and the like.

In addition, two or more N-long chain acylamino acid antimicrobial metal salts do not adhere to one inorganic particle as described above, and as an antimicrobial material, N-long chain acylamino acid salt of a metal having a first antimicrobial action on the surface of the inorganic particle. The first antimicrobial inorganic particles attached by the hydrophilic organic material and the second N-long chain acylamino acid salt having different antimicrobial activity from the first inorganic particles are formed by the hydrophilic organic material on the surface of the inorganic particles. It may consist of a mixture with the attached second antimicrobial inorganic particles.

That is, two kinds of inorganic particles to which different N-long-chain acylamino acid antimicrobial metal salts (for example, N-long-chain acylamino acid silver and N-long-chain acylamino acid copper) adhered may be mixed.

In this antimicrobial material, the use of the N-long-chain acylamino acid antimicrobial metal salt suitably used, the combination of these combinations, the compounding ratio, etc. can be changed suitably according to the purpose of use.

Next, the 2nd antimicrobial material of this invention is demonstrated.

This antibacterial material has N-long-chain acylamino acid which adhered to the surface of a synthetic resin particle or an inorganic particle, Furthermore, the N- long-chain acylamino acid becomes the N-long-chain acylamino acid water-insoluble salt couple | bonded with the metal which has antibacterial effect. .

More specifically, the antimicrobial agent binds to the N-long-chain acylamino acid directly attached to the surface of the synthetic resin particle, and after the N-long-chain acylamino acid is attached, the metal having an antimicrobial action and N-long-chain acylamino acid bind to the synthetic resin particles. The N-long-chain acylamino acid antimicrobial metal salt formed on the surface adheres.

That is, in this antimicrobial action substance, the N-long-chain acylamino acid water-insoluble salt of the metal which has the antibacterial effect formed in the surface of a particle | grain is attached to the surface of synthetic resin particle | grains or an inorganic particle.

In the antimicrobial material of the present invention, the synthetic resin particles or the inorganic particles can easily control the particle size of the antimicrobial material to be formed, and at the same time, the specific gravity can also be selected according to the purpose. I can write it.

Further, by using the synthetic resin particles, the particle size and specific gravity can be selected as described above, so that the formed antimicrobial material can be easily added to resins, fibers, paints and the like. That is, dispersibility may not be enough only with N-long-chain acylamino acid antimicrobial metal salt, and dispersibility improves.

The synthetic resin particles may be any one as long as the particles can be formed.

Moreover, the property of particle | grains differs by the objective to which antibacterial material is added.

In general, polystyrene particles, polyolefin particles (polyethylene, polypropylene), polyvinyl acetate particles, polyester particles, crosslinked polystyrene particles, polyamide particles, polymethacryl, from the stability, dispersibility, uniformity of particle shape, particle size, etc. Rate particles, fluorine resin particles and the like are suitable. Particularly, polystyrene particles and crosslinked polystyrene particles are suitable.

Moreover, it is preferable that the surface cationized, and the thing which carried out the cation treatment of the said microparticles | fine-particles is suitable.

As a cation treatment, surface treatment is performed by a cationic surfactant, treatment by a cationic treatment agent (for example, alumina treatment), or the like.

As the inorganic particles, those whose surfaces are cationized, that is, those having a positively charged surface, are used. Furthermore, alumina particles, silica-alumina particles, which are ceramic particles and have a positively charged surface, are suitable due to the obtaining of stability, dispersibility, particle shape, uniformity of particle diameter, and fine particles.

Especially preferred are silica-alumina particles.

In addition, cationic treatment of inorganic fine particles whose surface is not cationized is also suitable.

As a cation treatment, surface treatment with a cationic surfactant, treatment with a cationic treatment agent (for example, alumina treatment), and the like are performed.

As the inorganic fine particles to be subjected to cation treatment, ceramic particles, fine titanium powder (for example, fine titanium oxide powder), fine calcium carbonate powder and the like are suitable.

In addition, since the above-mentioned N-long-chain acylamino acid becomes an anion in the state dissolved in water, since N-long-chain acylamino acid adheres to the surface of the inorganic particle which has a positive charge, the hydrophilic organic substance as mentioned above is not used. You don't have to.

And as a particle size of particle | grains, although it changes with the use using the antimicrobial material of this invention, it is generally about 0.01 micrometer-1 mm, Preferably it is about 0.1 micrometer-10 micrometers.

For example, when it aims at the spread to a growth site, such as a mold, a thing with a rather big particle | grain can be used, and if it demonstrates concretely, it is about 1 mm or less.

In addition, in the case where the antimicrobial material of the present invention is mixed in the resin, the thickness is preferably 1 to 0.01 µm in order not to alienate the transparency of the resin to be mixed.

Moreover, also when mixing the antimicrobial material of this invention in a foam, about 1 micrometer or less, More preferably, it is 1-0.01 micrometer. Moreover, also when disperse | distributing in paper, about 1 micrometer or less, More preferably, it is 1-0.01 micrometer. Also in the case of dispersing in Tokyo, it is about 1 µm or less, more preferably 1 to 0.01 µm. As for the ratio of particle | grains and N- long chain acylamino acid salt, the higher the level which antibacterial property is calculated | required, the content of N- long chain acyl amino acid salt increases. In general, the mixing ratio of the particles and the N-long-chain acylamino acid salt is preferably about 1000: 1 to 1: 1 by weight.

N-long-chain acylamino acid is water-soluble before it combines with the metal which has antimicrobial property, and has surfactant activity at the same time. For this reason, it adheres directly to the surface of synthetic resin.

The N-long chain acylamino acid may be directly attached to the synthetic resin particles, but as described above, a hydrophilic organic material may be used to adhere to the surface of the synthetic resin particles.

As for the N-long-chain acylamino acid antimicrobial metal salt, those mentioned above may be suitably used. As with the inorganic particle antimicrobial material using the hydrophilic organic substance mentioned above, it is preferable that two or more types of N-long-chain acylamino acid salts bonded to other metals having an antimicrobial action adhere to the surface of the synthetic resin particle or the inorganic particle.

That is, it is preferable that two or more types of N-long-chain acyl amino acid salts adhere to a particle | grain, and these N- long-chain acyl amino acid salts bind | couple the other metal which has antimicrobial property.

As the antimicrobial metals and combinations thereof, those mentioned above are preferable.

As described above, two or more N-long-chain acylamino acid antimicrobial metal salts do not adhere to one particle, and as an antimicrobial material, N of a metal having a first antimicrobial effect on the surface of synthetic resin particles or inorganic particles. -First antimicrobial particles attached by a long chain acylamino acid salt and a hydrophilic organic substance, and a second N-long chain acyl amino acid salt having a metal having an antimicrobial action with the first antimicrobial particles is a synthetic resin particle or an inorganic particle. It may consist of a mixture with the first antimicrobial particles attached to the surface of the substrate by a hydrophilic organic substance.

That is, two kinds of particles to which different N-long-chain acylamino acid antimicrobial metal salts (for example, N-long-chain acylamino acid silver and N-long-chain acylamino acid copper) adhered may be mixed.

As this antimicrobial material, according to the purpose of use, the selection of the N-long-chain acylamino acid antimicrobial metal salt suitably used, the selection of these combinations, the compounding ratio, etc. can be changed suitably.

And the manufacturing method of the antimicrobial material of this invention is demonstrated.

The method for producing a first antimicrobial material of the present invention comprises the steps of attaching a hydrophilic organic material to the surface of an inorganic particle, contacting the particles having a hydrophilic organic material adhered to the surface with an N-long chain acylamino acid ion-containing aqueous solution, After the step, the particles are brought into contact with a metal ion-containing aqueous solution having an antibacterial effect.

Each process is demonstrated.

As the inorganic particles, those mentioned above are suitably used.

First, in the step of attaching the hydrophilic organic material to the surface of the inorganic particles, an aqueous solution of the hydrophilic organic material (for example, an aqueous PVA solution) is prepared as described above, and the aqueous solution is dispersed in the inorganic particles or the inorganic particles in the aqueous solution By dipping.

As a density | concentration of a hydrophilic organic substance in aqueous solution, about 0.001 to 5 weight% is suitable.

Then, it is preferable to spray the hydrophilic organic material aqueous solution on the surface of the inorganic particles or to immerse the inorganic particles in the aqueous solution, followed by drying.

As drying temperature, it is preferable to carry out about 30 to 24 hours at about 40-100 degreeC.

In this way, the hydrophilic organic substance adhered to the surface of the inorganic particles is formed.

Subsequently, the particles having the hydrophilic organic substance adhered to the surface are brought into contact with an N-long chain acylamino acid ion-containing aqueous solution. And you may dry as needed.

The preparation of the N-long chain acylamino acid ion-containing aqueous solution is rinsed by dissolving N-long chain acylamino acid or water-soluble N-long chain acylamino acid salt in water.

As N-long-chain acylamino acid or a water-soluble N-long-chain acylamino acid salt, N-stearoyl glutamic acid, N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-stearoyl asparaginic acid, N-lauroyl aspartic acid , N-myristoyl aspartic acid, N-stearoyl valine, N-lauroyl valine, N-mirrostoyl valine, N-stearoyl phenyl alanine, N-lauroyl phenyl alanine, N-mirrostoyl Phenyl alanine, N-stearoyl arginine, N-lauroyl arginine, N-mirastoyl arginine and their alkali metal salts (eg sodium, potassium) and the like are suitably used.

As an N-long-chain acylamino acid or water-soluble N-long-chain acylamino acid salt concentration in an aqueous solution, about 0.001 to 5 weight% is suitable.

Then, the inorganic particles to which the hydrophilic organic substance and the N-long-chain acylamino acid or the water-soluble N-long-chain acylamino acid are attached are combined with the N-long-chain acylamino acid to form an insoluble salt in water. Contact with aqueous solution.

Specifically, a water-soluble salt of a metal having antimicrobial properties, for example, silver nitrate, copper nitrate, silver sulfate, silver soluble aqueous solution such as copper chloride, copper sulfate, zinc nitrate, zinc chloride, bismuth nitrate, etc. Is carried out by scattering the inorganic particles or immersing the inorganic particles in an aqueous solution.

As a concentration of the water-soluble salt of the metal which has antimicrobial property in aqueous solution, about 0.001 to 5 weight% is suitable. By this step, the N-long-chain acylamino acid ion and the antimicrobial metal ion adhered to the surface of the inorganic particle are bonded, and the N-long-chain acylamino acid antimicrobial metal salt insoluble in water is formed on the surface of the particle. The aqueous solution is preferably dried after immersing the inorganic particles in a dispersion or an aqueous solution.

As drying temperature, it is about 40-100 degreeC, and it is preferable to carry out about 30 minutes-about 24 hours. In this way, the hydrophilic organic substance adhered to the surface of an inorganic particle is formed.

In the method for producing the antimicrobial agent, the N-long-chain acylamino acid antimicrobial metal salt, which is insoluble in water formed in advance and in the form of a powder, is not attached to the surface of the particles. The long-chain acylamino acid antimicrobial metal salt is formed. This makes the attachment work easy.

When the N-long-chain acylamino acid antimicrobial metal salt is formed in advance, since the N-long-chain acylamino acid antimicrobial metal salt aggregates in the formation process, the aggregate which N-long-chain acylamino acid antimicrobial metal salt aggregated also forms in the formed powder.

For this reason, in N-long-chain acylamino acid antimicrobial metal salt powder, some part of much more of an antimicrobial metal may be in the state which does not expose to a surface.

In this case, it is anticipated that sufficient thing is not exhibited as an antibacterial effect.

In contrast, in the antimicrobial agonist prepared by this method, N-long-chain acylamino acid is attached and then contacted with an antimicrobial metal ion-containing aqueous solution as a final step, and at the same time, N-long-chain acylamino acid antimicrobial metal salt is formed on the surface of the particles. The N-long-chain acylamino acid antimicrobial metal salt is less likely to cause aggregation of the N-long-chain acylamino acid antimicrobial metal salt. It is assumed to be.

For this reason, the high antibacterial effect which N-long-chain acylamino acid antimicrobial metal salt has is fully exhibited.

Moreover, N-long chain acylamino acids are so-called surfactants and adhere almost uniformly to the surface of the particles. For this reason, the coating of N-long-chain acylamino acid which is substantially uniform and coat | covers the whole is formed in the surface of particle | grains, and since the metal bonds, the film of N-long-chain acylamino acid antimicrobial metal salt formed also shows the whole surface of particle | grains. At the same time, it becomes uniform.

Furthermore, this process is carried out by contacting the inorganic particles with an aqueous solution containing two or more other metal ions having an antimicrobial action, or by contacting the first metal ion-containing aqueous solution with an antibacterial action and then removing the antimicrobial action. It is preferable to carry out by making it contact with the metal ion which has a metal ion containing aqueous solution which has another 2nd antibacterial effect. In particular, the former is preferable.

In the former case, water-soluble salts of metals having antimicrobial properties, for example, silver nitrate, copper nitrate, silver sulfate, and two or more water-soluble salts having different metals are selected from copper chloride, copper sulfate, zinc nitrate, zinc chloride, bismuth nitrate, and the like. A mixed metal ion-containing aqueous solution to which these are added is prepared, and this aqueous solution is rinsed by scattering the inorganic particles or immersing the inorganic particles in the aqueous solution.

In the latter case, inorganic particles are sequentially contacted with another metal salt aqueous solution (application of aqueous solution or immersion in aqueous solution).

By doing in this way, the surface of particle | grains can form the antimicrobial action substance which two or more types of antimicrobial metal salts adhered to. Compared with only one type of antimicrobial metal, it has a broader antimicrobial spectrum, has a higher antimicrobial effect, and exhibits an antimicrobial effect against more types of fungi. Moreover, two or more types of N-long-chain acylamino acid salts are salts of the metal which has antibacterial effect, and N-long-chain acylamino acid, at least metal differs, and N-long-chain acylamino acid is the same, or another Also good. In view of antibacterial activity and safety, silver or copper is an essential metal, and at least one of other metals (silver, copper, lead, zinc, tin, bismuth, etc.) is preferably selected and used.

Moreover, as a more preferable combination, silver or copper is used as an essential metal, and 2 or more types are selected and used from another metal (silver, copper, lead, zinc, tin, bismuth, etc.).

Specific examples of preferred combinations include silver and copper, silver and zinc, silver and lead, copper and zinc, silver and copper and zinc, silver and copper and lead, silver and copper and bismuth, copper and zinc and lead and the like.

Next, the manufacturing method of the 2nd antimicrobial substance of this invention is demonstrated.

The method for producing an antimicrobial agent has a step of bringing synthetic resin particles or inorganic particles into contact with an N-long-chain acylamino acid ion-containing solution, and thereafter a step of contacting the particles with a metal ion-containing aqueous solution having an antibacterial action. have.

As the synthetic resin particles, the above-mentioned ones are suitably used, and as the inorganic particles, the above-mentioned ones having a cation surface are used.

First, the surface of synthetic resin particles or inorganic particles is brought into contact with an N-long chain acylamino acid ion-containing solution. As a result, N-long-chain acylamino acid adheres to the surface of the synthetic resin or the inorganic particles having a positive charge. And you may dry as needed.

In this step, the preparation of the N-long chain acylamino acid ion-containing aqueous solution is prepared by dissolving N-long chain acylamino acid or a water-soluble N-long chain acylamino acid salt in water.

As N-long-chain acylamino acid or water-soluble N-long-chain acylamino acid salt, the above-mentioned thing is used suitably. As an N-long chain acylamino acid or aqueous solution N-long chain acylamino acid salt concentration in an aqueous solution, about 0.01-5 weight% is suitable. And you may dry as needed.

And the particle | grains which N-long-chain acylamino acid ion or water-soluble N-long-chain acylamino acid adhered are contact | connected with the antimicrobial metal ion containing aqueous solution which combines with the N-long-chain acylamino acid and forms insoluble salt in water. .

Specifically, this step prepares an aqueous solution of a water-soluble salt of a metal having antibacterial properties, such as silver nitrate, copper nitrate, silver sulfate, copper chloride, copper sulfate, zinc nitrate, zinc chloride, bismuth nitrate, This aqueous solution is dispersed by particles or by dipping the particles in the aqueous solution. As a density | concentration of a metal salt in aqueous solution, about 0.01 to 5 weight% is suitable.

In this step, the N-long-chain acylamino acid ions adhering to the surface of the particles and the antimicrobial metal ions are bonded to each other, and an N-long-chain acylamino acid antimicrobial metal salt insoluble in water is formed on the surface of the particles. And it is preferable to dry, after spraying the said aqueous solution or immersing particle in aqueous solution.

As drying temperature, it is preferable to carry out about 30 to 24 hours at about 40-200 degreeC. In this way, antimicrobial particles having N-long chain acylamino acid antimicrobial metal salts formed on the surface are formed.

In the method for producing the antimicrobial action substance, the N-long-chain acylamino acid antimicrobial metal salt is formed on the surface of the particle, just as the above-described inorganic particles are used.

Furthermore, it is assumed that N-long-chain acylamino acid antimicrobial metal salt adheres to the surface of the particle in a single molecule or in a state close thereto, and at the same time, the antimicrobial metal is exposed.

For this reason, the high antibacterial effect which N-long-chain acylamino acid antimicrobial metal salt has is fully exhibited.

Moreover, N-long chain acylamino acids are so-called surfactants and adhere almost uniformly to the surface of the particles. For this reason, the coating of N-long-chain acylamino acid which is almost uniform and coat | covers the whole is formed in the surface of particle | grains, and since the metal couple | bonds, the film of N-long-chain acylamino acid antimicrobial metal salt formed also has the whole surface of a particle | grain. At the same time, it becomes almost uniform.

Furthermore, this process is carried out by contacting the synthetic resin particles or the inorganic particles with an aqueous solution containing two or more other metal ions having an antimicrobial action, or by contacting the aqueous solution containing a metal ion having an antibacterial action and then having the antibacterial action. It is preferable to carry out by making it contact with the metal ion containing aqueous solution which has an antibacterial effect different from a metal ion.

In this regard, the same method as that for producing the antimicrobial agent using the inorganic particles described above is the same.

Next, the resin composition containing the antibacterial material of the present invention and the antimicrobial resin molded article will be described.

This resin composition contains the said antibacterial material.

As an addition amount of the antimicrobial material in an antimicrobial resin composition, about 0.05 to 5 weight% is preferable with respect to the total resin weight, More preferably, it is 0.1% to 3%. Moreover, when using the antimicrobial resin composition of this invention as an additive (for example, a high density pellet) in order to give antimicrobial property to another general resin, it is necessary to contain an antimicrobial material at a higher concentration.

As the addition amount of the antimicrobial action substance in this case, it is preferable to add to the limit which can be added to resin, for example, it is preferable to contain about 1 to 20 weight%.

As the resin material used in the antimicrobial resin composition of the present invention, any resin can be used, for example, a polyolefin resin (for example, polypropylene, polyethylene, polybutylene, ethylene-propylene copolymer), chloride Vinyl resin, styrene resin, urethane resin, silicone resin, polyamide, polyvinylidene (e.g. polyvinylidene chloride, polyvinylidene fluoride), polyester, further, polyurethane, polyethylene, polystyrene, poly Propylene, an epoxy resin, etc. can be used, and the antimicrobial resin composition of this invention is created by adding the above-mentioned antimicrobial material to said resin material.

As a specific resin composition, for example, a known vinyl chloride resin can be used, and as the vinyl chloride resin component, a homopolymer of vinyl chloride resin, furthermore, polyvinylidene chloride and vinyl chloride, preferably 90 mol% or more, Is a copolymer containing a monomer containing 95 mol% or more and capable of simultaneously copolymerizing with another copolymer (for example, vinylidene chloride, ethylene, propylene, vinyl acetate, etc.), and as the plasticizer, dibutyl phthalate , Phthalic acid esters such as dinuxyl phthalate, di-2-ethyl nuxyl phthalate, aliphatic polybasic acid esters such as dioctyl adipate, dioctyl azelate, dioctyl selcate, epoxidized soybean oil, epoxidized linseed oil, and the like Animal and vegetable oils are added, and as needed, those in which stabilizers, lubricants, and even other additives are blended are used. As the stabilizer, conventionally, metal soaps made of metals such as barium, zinc and calcium and higher fatty acid salts such as stearic acid and lauryl acid have been used, but N-long chains of metals having antibacterial properties used in the present invention Acylamino acid salt also has a function as this stabilizer, and can also omit said conventional stabilizer.

The antimicrobial resin composition of the present invention is prepared by mixing the above-described antimicrobial material with the vinyl chloride resin base, like a plasticizer and other additives.

The antimicrobial agent may be prepared by, for example, adding the plasticizer in advance, adding the same to the vinyl chloride resin base with other additives, and mixing the antimicrobial agent with a high concentration of the antimicrobial agent to the vinyl chloride resin (including the plasticizer). The addition of the ash may be prepared, and the vinyl chloride resin containing the antimicrobial agent at a high concentration may be added to the vinyl chloride resin containing no antibacterial material and kneaded.

In addition, a known polyolefin can be used as the resin material, and as the polyolefin, for example, monomers such as ethylene homopolymer and propylene homopolymer or random and block copolymers thereof can be used. Tablets (eg benzotriazoles), phenolic sulfates, neutralizers, lubricants, nucleating agents and the like are added as necessary.

The antimicrobial substance is then added to the polyolefin like the necessary additives and mixed, for example, formed into pellets.

In addition, a pellet prepared by adding an antimicrobial substance at high concentration to polyolefin was prepared, and as the antimicrobial resin composition of the present invention, the master pellet containing the antimicrobial substance at high concentration was mixed with other polyolefin pellets containing no antimicrobial substance. When preparing a resin molding suitably, you may mix in a mixer and produce the resin molding according to the objective.

As the antimicrobial resin moldings, various ones formed using the above antimicrobial resin compositions are considered, for example, stationery, toys, plastic tableware, packaging containers, packaging materials (eg, films), tapes, sheets, and the like. , Nets, pipes, hoses, trays and containers.

Next, an antimicrobial bath having an antimicrobial inner surface whose inner surface is formed of a synthetic resin containing the above antimicrobial material will be described.

At least the inner surface of the antimicrobial bath of the present invention is formed of a synthetic resin containing the above antimicrobial material.

As the synthetic resin used in the antimicrobial bath, those which are colorless and transparent, such as acrylic resins (for example, AS and ABS) and polycarbonate, and which have a certain degree of strength are suitably used.

The antimicrobial bath is sufficient if its inner surface has antimicrobial properties.

A bath having only such an inner surface as an antimicrobial agent is, for example, a resin having a high adhesiveness with the synthetic resin on the inner surface of the synthetic resin forming the tank, preferably a resin homogeneous or similar to the resin forming the tank. It can form by coating the resin mold containing an antimicrobial material.

In this case, the content of the antimicrobial agent in the resin of the surface layer containing the antimicrobial material is considered to have sufficient antimicrobial activity, preferably 0.005% or more, preferably 0.05% or more, based on the resin weight of the surface layer. It is -1%. Moreover, you may form a water tank agent using what contains the said antibacterial material in the whole resin.

As content of the antibacterial substance in resin, when it is 0.05% or more with respect to resin weight, Preferably it is 0.05% or more, it is considered that there exists sufficient antibacterial effect, Preferably it is 0.1 to 1%.

In the water tank of the present invention, since the antibacterial material contained in the resin forming the inner surface has been described above, it is possible to safely generate green algae and the like over a long period of time without adversely affecting fish and shellfish stored in the water tank, The adhesion can be prevented. And this antimicrobial tank can be used for various destruction tanks, such as an aquarium, a school, a restaurant, and a household.

Next, the antimicrobial paint of the present invention will be described.

The antimicrobial paint of the present invention contains the above antibacterial material.

And as a coating material used for the antimicrobial paint of this invention, a fatty acid paint, an epoxy resin paint, a solvent-free epoxy resin paint, a vinyl ester paint, a polyurethane resin paint, a solvent-free polyurethane resin paint, Furthermore, a silicone resin paint, fluorine Resin coating materials;

Moreover, as content of said antimicrobial substance in the antimicrobial paint of this invention, it is preferable to contain about 0.01%-about 10%, and 0.1 to 5% is especially preferable.

The antimicrobial paint of the present invention is that the antimicrobial agent contained has N-long-chain acylamino acid salt as the long antimicrobial substance as described above, and this salt has a basic skeleton of amino acid, high safety, and further forms a salt. As the metal present, those having high antimicrobial properties can be used.

Therefore, when used as antifouling paint, adhesion of aquatic organisms to water (including seawater) contact portions in ships and underwater structures is prevented.

As a coating material when the coating material of this invention is applied to antifouling paint, a well-known thing can be used, For example, in a 1-component type coating material, as a resin component, rosin, an acrylic resin, an oil-based resin, a vinyl chloride-type resin, synthetic Rubber type resin, chlorinated polyylstyrene resin, etc., As a plasticizer, Phosphoric acid ester type, such as a tricredi phosphate and a triphenyl phosphate, di-n- dodecyl phthalate, a dinonyl phthalate. Phthalic acid esters such as di-2-ethylhexyl phthalate, di-n-butyl phthalate, dimethyl phthalate, chlorinated paraffin and polyester, and the like. As the organic solvent, for example, aromatic hydrocarbon solvents such as xylene and toluene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are used, and the above-described antibacterial material is added to these coating materials.

Moreover, as a two-component coating, well-known things, such as the above-mentioned epoxy resin paint, a solventless epoxy resin paint, a polyurethane resin paint, and a solventless polyurethane resin paint, can be used, For example, as an epoxy resin paint material, a bisphenol-type epoxy Resins, cyclic aliphatic epoxy resins, phenol or cresol novolac type epoxy resins, phthalic acid glycidyl ester type epoxy resins, polyglycol type epoxy resins, and the like, and, if necessary, thermosetting resins or thermoplastic resins compatible with these epoxy resins, etc. Is added.

Moreover, as a hardening | curing agent mixed with the said resin liquid at the time of use, hardening | curing agents for epoxy resins, such as aromatic amine, polyalkylene polyamine, polyamide, and amine modified amide which are poorly soluble in water and substitutable with water molecules, are used. Furthermore, as a polyurethane coating material, a well-known thing can be used similarly, It is a two-component type which consists of a polyol and polyisocyanate, As a polyol, For example, ethylamine, butylamine, diaminodiphenylmethane, hexaethylenediamine, etc. Reaction products of an amino compound with an epoxy compound such as diglycidyl phthalate, epoxy butane, butyl glycidyl ether, polyethyleneglycidyl ether, and the like can be used, and examples of the polyisocyanate include diphenylmethane diisocyanate, Isocyanate group-containing prepolymers using dicyclohexyl methane diisocyanate, triylene diisocyanate, and hexamethylene diisocyanate are used.

The antibacterial material of the above-mentioned quantity is added to such coating material.

Moreover, when using the above-mentioned two-component thing as a coating material, you may add an antibacterial material to the one or both. Preferably, the antimicrobial agent is added to the epoxy resin liquid in the two-component epoxy paint and to the polyol in the two-component polyurethane paint by adding it to the coating component side of the side which is less likely to give modification to the added antimicrobial material. It is preferable to add.

In addition, the antimicrobial paint of the present invention is not limited to the antifouling paints as described above, and can be widely used for interior and exterior wall surfaces and floors such as schools, hospitals, offices, food factories, and general houses (eg, kitchens, bathrooms). As the coating material, either an aqueous or oily material can be used.

Next, the paper which has antibacterial property of this invention is demonstrated.

As for the paper which has antimicrobial property of this invention, the above-mentioned antimicrobial material adheres to the surface, or contains the antimicrobial material inside.

As the paper material to be used, any one of the sun paper and Japanese paper may be used, and as the antimicrobial paper, for example, hybrid paper, leaf paper (for example, tissue paper, tissue paper, toilet paper, napkin or towel paper, sanitary paper), Wrapping paper, coated paper (for example, art paper, coated paper), non-coated paper, printed paper, drawing paper, etc., and paperboard, such as single ball paper, buck paper, yellow paper, slab paper, chip ball, corrugated paper, banknote paper, earth Etc.

The antimicrobial paper contains, for example, an antimicrobial agent attached or adhered to a paper surface, and the antimicrobial material is formed of N-long chain acylamino acid salt of a metal having an antimicrobial action as described above. As a method of adhering an antimicrobial agent to the surface of paper, it can be performed by containing an antimicrobial agent in the substance which has adhesiveness with respect to the paper surface, and apply | coating a foreign material (liquid phase) to the surface of paper.

As such a method, for example, in the case of an aqueous system, a cellulose-based powder having fixability, such as carboxymethyl cellulose, methyl cellulose, oxypropyl cellulose, oxyethyl cellulose, PVA (polyvinyl alcohol), PVP (polyvinylpyrrolidone) And an antimicrobial agent contained in an aqueous solution such as vinylpyrrolidone-vinyl acetate copolymer.

In the case of hydrophobic resins, an antimicrobial agent may be used in a silicone resin coating agent (for example, a dimethylsiloxane coating agent, a methylhydrodiene polysiloxane coating agent, a methyl trichlorosiloxane coating agent, a silane coupling agent), and a fluororesin coating agent. It is created by coating and drying what was contained on the surface of paper.

As such, the amount of adhesion in the case of adhering the antimicrobial material to the surface of the paper is preferably about 0.005 to 5 g / m 2, more preferably about 0.01 to 1 g / m 2.

Moreover, as a preparation method of the antimicrobial paper which contains an antimicrobial material in the inside of a paper, it can carry out by making paper using the thing which contained the antimicrobial material in the manufacturing stock solution.

Thus, as addition amount in the case where paper contains an antimicrobial agent, about 0.05%-3% of the weight of paper are suitable, More preferably, it is about 0.1-1%.

Then, the specific example of the method of adhering the said antimicrobial material to the surface of paper is demonstrated.

In order to perform this method, it is necessary to prepare a surface treatment agent for coating on the surface of paper, and first, a substance (adhesive material) having adhesion to the surface of the paper is used, for example, carboxymethyl cellulose, methyl cellulose, Oxypropyl cellulose, oxyethyl cellulose, PVA (polyvinyl alcohol), modified PVA (e.g., carboxy modified PVA, sulfonic acid modified PVA, acrylamide modified PVA, carion group modified PVA, long chain alkyl group modified PVA), starch, modified starch , Kazenin, synthetic resin emulsions (e.g., styrene-butadiene latex, polyacrylic acid ester emulsion, vinyl acetate-acrylic acid ester copolymer emulsion, vinyl acetate-ethylene copolymer copolymer emulsion), and the like, and the concentration in the surface treatment agent is a surface treatment target. Although it depends on the kind of paper etc., about 0.1 to 30 weight% is suitable.

And the antibacterial material mentioned above is added to this surface treating agent.

As addition amount, about 0.05 to 5% is good, More preferably, it is about 0.1 to 1%.

As the surface treatment agent, water-repellents such as glyoxal and urea resins, plasticizers such as glycols and glycerin, pH adjusters such as ammonia, caustic soda, sodium carbonate or phosphoric acid, defoamers, mold release agents, surfactants, etc. Known additives may be added.

The above-mentioned additive is added to a required solvent, such as water, and sufficiently stirred to prepare a surface treating agent having an antibacterial effect.

The paper to be applied is not particularly limited, but the above-mentioned wallpaper, the above-described wrapping paper, uncoated paper, printing paper, drawing paper, single-bolt paper, white paper, yellow paper, color paper, chip ball, corrugated paper, banknote paper, There are lands. Moreover, a well-known method can be used as a coating method of a surface treating agent, For example, arbitrary methods, such as a size press coater, a roll coater, an air knife coater, a blend coater, can be used.

Although the coating amount varies with the purpose, about 0.1-30 g / m <2> of solid content is suitable.

Next, the cosmetics of this invention are demonstrated.

The cosmetics of this invention contain said antimicrobial material.

As cosmetics which are the object of this invention, cosmetics, milky milk, etc. are mentioned as a basic cosmetics, for example.

Examples of the finished cosmetics include powder powder, solid powder, foundation, cheek oil, and the like. Facial cleansing agents include, for example, cosmetic soap and the like, and toothpaste and the like can be considered.

As the amount of the antimicrobial agent incorporated into cosmetics, for example, when added to cosmetic cream or milky liquid, 0.01 to 5% is good.

Cosmetic creams include oily creams (e.g., varnishing creams, after shave creams, creams under makeup), neutral creams (e.g., moisturizing creams), oily creams (e.g., cold creams), and the like. The antimicrobial agent of may be added to any of them, and may be added to a mixture of oils (such as fatty acids, higher alcohols) or glycerin in the cream in advance.

After the cream is prepared, it may be added and kneaded.

Moreover, since this antimicrobial material has antimicrobial property, it also functions as a cream preservative, and therefore, it is not necessary to add a preservative separately.

Moreover, as addition amount in the case of mixing in powdered powder and intrinsic powder, 0.01 to 10% is good and especially 0.1 to 5% is good.

Moreover, as an addition amount in the case of mixing in a foundation (for example, foundation cream, a foundation stick, a foundation cake, a ball roll), 0.01-5% is good, especially 0.05-2% is good.

In addition, toothpaste (e.g. powdered toothpaste, oily ( I) Toothpaste, toothpaste) is preferably 0.05 to 10%, particularly preferably 0.1 to 5%. Moreover, as addition amount in the case of mixing in a makeup soap, 0.05 to 10% is good, and 0.1 to 5% is especially preferable.

As other cosmetics, it can also be used in powders (for example, baby powder), medicinal cosmetics (for example, sunburn cream, deodorant cosmetics) and the like.

The amount of addition is preferably 0.01 to 5%, particularly preferably 0.05 to 3%.

In addition, the cosmetic product of the present invention can prevent the occurrence and progression of purulent dermatitis, acne, odor, eczema, and maintain the hygiene of the skin.

(Example)

Next, the specific example of the antimicrobial material of this invention is demonstrated.

(Example 1)

As inorganic particles, silica-alumina sintered particles (manufactured by ZEELAN Corporation, product number ZEEOSPHERES 200, average particle diameter of 1.3 mu m, specific gravity 2.1) were used.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

As a hydrophilic organic substance, 1 kg of inorganic particles were added and immersed in PVA aqueous solution in which 0.7 g of this PVA was dissolved in 5 liters of water using PVA (manufactured by Kuraray Chemical Co., Ltd., product name follicle 117, saponification degree 98.5%). Then, it took out and dried at about 70 degreeC for 24 hours, and produced the inorganic particle which PVA coated on the surface. Then, an N-long-chain acylamino acid aqueous solution in which 50 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and the entire amount of the inorganic particles with PVA was added to the aqueous solution and allowed to stand for some time.

Then, silver nitrate solution in which 28 g of silver nitrate was dissolved in 300 ml of water was added, left for a while, and then taken out and dried at about 70 ° C. for 24 hours, whereby PVA and N-stearoyl-L-glutamic acid were attached to the surface of the inorganic particles. About 1 kg of antibacterial material (Example 1) was obtained.

(Example 2)

As the inorganic particles, silica-alumina sintered particles (average particle size 1.3 mu m, specific gravity 2.1) as used in Example 1 were used.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

As a hydrophilic organic substance, 1 kg of inorganic particles were immersed in PVA solution in which 0.7 g of this PVA was dissolved in 5 liters of water using PVA (manufactured by Kuraray Co., Ltd., product name: 117, saponification degree 98.5%), and left for a while. Then, it took out and dried at about 70 degreeC for 24 hours, and produced the inorganic particle which PVA coated on the surface. Then, an N-long-chain acylamino acid aqueous solution in which 50 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and the entire amount of the inorganic particles with PVA was added to the aqueous solution and allowed to stand for some time.

Then, an aqueous copper nitrate solution in which 30 g of copper nitrate was dissolved in 300 ml of water was added, left for a while, then taken out, and dried at about 70 ° C. for 24 hours to dry PVA and N-stearoyl-L-glutamate on the surface of the inorganic particles. About 1 kg of an antimicrobial agent (Example 2) attached thereto was obtained.

(Example 3)

As the inorganic particles, silica-alumina sintered particles (average particle size 1.3 µm, specific gravity 2.1) as used in Example 1 were used.

As the N-long chain acylamino acid and the alkali metal salt, N-stearoyl-L-glutamic acid disodium (manufactured by Ajinomodo Co., Ltd., trade name Amisoft HS-21) was used.

As a hydrophilic organic substance, 1 kg of inorganic particles were immersed in PVA solution in which 0.7 g of this PVA was dissolved in 5 liters of water using PVA (manufactured by Kuraray Co., Ltd., product name: 117, saponification degree 98.5%), and left for a while. Then, it took out and dried at about 70 degreeC for 24 hours, and produced the inorganic particle which PVA coated on the surface. Then, an N-long-chain acylamino acid aqueous solution in which 50 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and the entire amount of the inorganic particles with PVA was added to the aqueous solution and allowed to stand for some time.

Then, an aqueous zinc nitrate solution in which 32 g of zinc nitrate was dissolved in 300 ml of water was added, left for a while, then taken out and dried at about 70 ° C. for 24 hours, whereby PVA and N-stearoyl-L-glutamic acid were applied to the surface of the inorganic particles. About 1 kg of zinc-containing antibacterial material (Example 3) was obtained.

(Example 4)

As the inorganic particles, silica-alumina sintered particles (average particle size 1.3 µm, specific gravity 2.1) as used in Example 1 were used.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

As a hydrophilic organic substance, PVA (made by Kuraray Co., Ltd., product name blasting 117, ignition degree 98.5%) was used, and 1 kg of inorganic particles was immersed in the PVA aqueous solution which 0.7 g of this PVA dissolved in 5 liters of water, and left to stand for some time. Then, it took out and dried at about 70 degreeC for 24 hours, and produced the inorganic particle which PVA coated on the surface. Then, an N-long-chain acylamino acid aqueous solution in which 50 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and the entire amount of the inorganic particles with PVA was added to the aqueous solution and allowed to stand for some time.

Then, a mixed solution of silver nitrate and copper nitrate, in which 10 g of silver nitrate and 17 g of copper nitrate was dissolved in 300 ml of water, was added and left for a while, then taken out and dried at about 70 ° C. for 24 hours. About 1 kg of antibacterial material (Example 4) to which royl-L-glutamic acid silver and N-stearoyl-L-glutamic acid copper were attached was obtained.

(Example 5)

The antimicrobial material of this invention (Example 5) was created by mixing 100 g of antimicrobial material of Example 1, and 100 g of antimicrobial material of Example 2.

(Example 6)

Polystyrene particles (manufactured by Sumidomo Chemical Co., Ltd., product number PB-3011W, average particle diameter 11.1 mu m, specific gravity 1.06) were used as the synthetic resin particles.

As the alkali metal salt of the N-long-chain acylamino acid, this N-stearoyl-L-glutamic acid di- sodium (N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21)) was used. An aqueous N-long-chain acylamino acid solution in which 6.5 g of sodium was dissolved in 9 L of water was prepared.

An aqueous silver nitrate solution was prepared by dissolving about 4 g of silver nitrate in 900 ml of water using silver nitrate as the water-soluble salt of the metal having antimicrobial properties.

First, 100 g of synthetic resin particles are added to an aqueous N-long chain acylamino acid solution, immersed and stirred, and left to stand for about 60 minutes, then taken out and dried at about 60 ° C. for about 24 hours, where the N-long chain acyl amino acid is attached to the surface. Particles were created.

The total amount of the synthetic resin particles was added to 900 ml of the aqueous solution of silver nitrate, immersed and stirred, allowed to stand for 60 minutes, then taken out, dried at 60 ° C. for about 24 hours, and N-stea on the surface of the synthetic resin particles. About 100 g of antibacterial material (Example 6) to which royl-L-glutamic acid silver was attached was obtained.

(Example 7)

As the synthetic resin particles, the same polystyrene particles (average particle size 11 µm, specific gravity 1.06) used in Example 6 were used.

As the alkali metal salt of the N-long-chain acylamino acid, this N-stearoyl-L-glutamic acid di- sodium (N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21)) was used. An aqueous N-long-chain acylamino acid solution in which about 4 g of sodium was dissolved in 9 L of water was prepared.

Using copper nitrate as a water-soluble salt of a metal having antimicrobial activity, an aqueous copper nitrate solution was prepared in which about 3 g of copper nitrate was dissolved in 900 ml of water.

First, 100 g of synthetic resin particles are added to an aqueous N-long chain acylamino acid solution, immersed and stirred, left to stand for 60 minutes, then taken out and dried for about 24 hours at 60 ° C., and the N-long chain acyl amino acid is attached to the surface. Particles were created.

Then, the entire amount of the synthetic resin particles was added to 900 ml of the above aqueous solution of copper nitrate, immersed and stirred, and left to stand for about 60 minutes, then taken out, dried at 60 ° C. for about 24 hours, and the surface of the synthetic resin particles was treated with N-. About 100 g of an antimicrobial material (Example 7) with stearoyl-L-glutamic acid copper was obtained.

(Example 8)

As the synthetic resin particles, the same polystyrene particles (average particle size 11 µm, specific gravity 1.06) as used in Example 6 were used.

As the alkali metal salt of the N-long-chain acylamino acid, this N-stearoyl-L-glutamic acid di- sodium (N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21)) was used. An aqueous N-long-chain acylamino acid solution in which about 4 g of sodium was dissolved in 9 L of water was prepared.

Zinc chloride solution was prepared by dissolving about 3.5 g of zinc chloride in 900 ml of water using zinc chloride as a water-soluble salt of an antimicrobial metal.

First, 100 g of synthetic resin particles are added to an aqueous N-long chain acylamino acid solution, immersed and stirred, and left to stand for about 60 minutes, then taken out and dried at about 60 ° C. for about 24 hours, where the N-long chain acyl amino acid is attached to the surface. Particles were created.

Then, the whole amount of the synthetic resin particles was added to 900 ml of the above zinc chloride aqueous solution, immersed and stirred, left for 60 minutes, then taken out, dried at 60 ° C. for about 24 hours, and the surface of the synthetic resin particles was treated with N-. About 100 g of an antibacterial material (Example 8) to which stearoyl-L-glutamate was attached was obtained.

(Example 9)

As the synthetic resin particles, the same polystyrene particles (average particle size 11 µm, specific gravity 1.06) as used in Example 6 were used.

As the alkali metal salt of the N-long-chain acylamino acid, this N-stearoyl-L-glutamic acid di- sodium (N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21)) was used. An aqueous N-long-chain acylamino acid solution in which about 4 g of sodium was dissolved in 9 L of water was prepared.

Silver nitrate and copper nitrate were used as water-soluble salts of metals having antimicrobial properties. A mixed aqueous solution of silver nitrate and copper nitrate was prepared by dissolving about 1.2 g of silver nitrate and about 2 g of copper nitrate in 900 ml of water.

First, 100 g of synthetic resin particles are added to an aqueous N-long chain acylamino acid solution, immersed and stirred, and left to stand for about 60 minutes, then taken out and dried at about 60 ° C. for about 24 hours, where the N-long chain acyl amino acid is attached to the surface. Particles were created.

The total amount of the synthetic resin particles was added to 900 ml of the mixed solution of silver nitrate and copper nitrate, immersed and stirred, and left for about 60 minutes, then taken out, dried at 60 ° C. for about 24 hours, and the surface of the synthetic resin particles. About 100 g of an antibacterial agent (Example 9) to which N-stearoyl-L-glutamic acid silver and N-stearoyl-L-glutamic acid copper were attached was obtained.

(Example 10)

Polystyrene particles (manufactured by Sumidomo Chemical Co., Ltd., product number PB-30061W, average particle diameter 6.1 mu m, specific gravity 1.06) were used as the synthetic resin particles.

As the alkali metal salt of the N-long-chain acylamino acid, this N-stearoyl-L-glutamic acid di- sodium (N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21)) was used. An aqueous N-long-chain acylamino acid solution in which about 4 g of sodium was dissolved in 9 L of water was prepared.

Silver nitrate and copper nitrate were used as water-soluble salts of metals having antimicrobial properties. A mixed aqueous solution of silver nitrate and copper nitrate was prepared by dissolving about 1.2 g of silver nitrate and about 2 g of copper nitrate in 900 ml of water.

First, 100 g of synthetic resin particles are added to an aqueous N-long chain acylamino acid solution, immersed and stirred, and left to stand for about 60 minutes, then taken out and dried at about 60 ° C. for about 24 hours, where the N-long chain acyl amino acid is attached to the surface. Particles were created.

The total amount of the synthetic resin particles was added to 900 ml of the mixed solution of silver nitrate and copper nitrate, immersed and stirred, and left for about 60 minutes, then taken out, dried at 60 ° C. for about 24 hours, and the surface of the synthetic resin particles. About 100 g of antibacterial material (Example 10) to which N-stearoyl-L-glutamic acid silver and N-stearoyl-L-glutamic acid copper were attached was obtained.

(Example 11)

The antimicrobial material of this invention (Example 11) was created by mixing 100 g of antimicrobial material of Example 6 and 100 g of antimicrobial material of Example 8.

(Example 12)

As inorganic particles, silica-alumina sintered particles (manufactured by ZEELAN Corporation, product number ZEEOSPHERES 200, average particle diameter of 1.3 mu m, specific gravity 2.1) were used.

And this inorganic particle has the electrostatic charge resulting from alumina.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 70 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

Then, an aqueous solution of silver nitrate, in which 28 g of silver nitrate was dissolved in 300 ml of water, was added, left for a while, and then taken out and dried for about 24 ° C. for 24 hours, whereby N-stearoyl-L-glutamic acid silver was attached to the surface of the inorganic particles. About 1 kg of ash (Example 12) was obtained.

(Example 13)

As the inorganic particles, the same ones as used in Example 12 were used.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 70 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

And after adding copper nitrate aqueous solution which melt | dissolved 30 g of copper nitrates in 300 ml of water, it was left to stand for some time, it was taken out, and it dried for about 70 degreeC for 24 hours, and copper N-stearoyl-L-glutamic acid was made to surface of an inorganic particle. About 1 kg of attached antimicrobial material (Example 13) was obtained.

(Example 14)

As the inorganic particles, the same ones as used in Example 12 were used.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 70 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

Then, zinc nitrate aqueous solution in which 32 g of zinc nitrate was dissolved in 300 ml of water was added, left to stand for some time, and then taken out and dried at about 70 ° C. for 24 hours, so that N-stearoyl-L-glutamate was added to the surface of the inorganic particles. About 1 kg of attached antimicrobial material (Example 14) was obtained.

(Example 15)

As the inorganic particles, the same ones as used in Example 12 were used.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 70 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

Then, an aqueous solution of silver nitrate and copper nitrate mixed with 10 g of silver nitrate and 17 g of copper nitrate dissolved in 300 ml of water was added, left for a while, taken out, and dried at about 70 ° C. for 24 hours, whereby N-stearoyl was applied to the surface of the inorganic particles. About 1 kg of antibacterial material (Example 15) to which -L-glutamic acid silver and N-stearoyl-L-glutamic acid copper were attached was obtained.

(Example 16)

0.5 parts by weight of glycerin monostearate and 1 part by weight of the antimicrobial material prepared in Example 1 were added to 100 parts by weight of polypropylene [melt index (230 ° C.), 2 g / 10 min, density = 0.905 g / cm 2), and a hexyl mixer was used. The mixture was mixed at 80 ° C for 2 minutes, strands were formed at 230 ° C by an extruder having a 40 mm diameter screw, and quenched to obtain strand cut pellets (master pellets, examples). Similarly, 0.5 parts by weight of glycerin monostearate was added to 100 parts by weight of polypropylene [melt index (230 ° C.), 2 g / 10 minutes, density = 0.905 g / cm 2), and the mixture was mixed at 80 ° C. for 2 minutes using a hexyl mixer. The strand was formed at 230 degreeC with the extruder which has a screw of 40 mm diameter, and it quenched and obtained cut pellet.

Then, 10 parts by weight of the master pellets were added to 100 parts by weight of the cut pellets, mixed at 80 ° C for 2 minutes using a Henschel mixer, and a strand was formed at 230 ° C by an extruder having a 40 mm diameter screw. It quenched and obtained strand cut pellet (Example).

The strand cut pellets were charged into an in-play line forming machine having a screw of 30 mm diameter, melt-molded at 250 ° C. to obtain an unoriented inflation film having a thickness of 120 μm.

Subsequently, the film was cut into 10 cm squares, stretched at the same time in a biaxially stretch measuring device at a temperature of 150 ° C. in two directions, 2.5 times each, and biaxially stretched polypropylene having an average thickness of 20 µm. A film was obtained.

(Example 17)

A biaxially stretched polypropylene film having an average thickness of 20 μm was obtained in the same manner as in Example 16 except that 0.5 parts by weight of the thing of Example 4 was added instead of the antibacterial material of Example 1 as the added antibacterial material.

(Example 18)

A biaxially stretched polypropylene film having an average thickness of 20 µm was obtained in the same manner as in Example 16 except that 2 parts by weight of the one of Example 6 was added instead of the antibacterial material of Example 1 as the added antibacterial material.

(Example 19)

A biaxially stretched polypropylene film having an average thickness of 20 µm was obtained in the same manner as in Example 16 except that 1 part by weight of the one of Example 10 was added instead of the antibacterial material of Example 1 as the added antibacterial material.

(Example 20)

70 parts by weight of di-2-ethylhexyl phthalate, 100 parts by weight of polyvinyl chloride with an average degree of polymerization of about 2300, 10 parts by weight of epoxidized soybean oil, 2 parts by weight of Ca-Zn-based stabilizer, 1 part by weight of lubricant, Example 4 (inorganic particles) 2 parts by weight of an antimicrobial agent was added, and a polyvinyl chloride sheet having a thickness of about 1 mm, a thickness of about 20 cm, and a length of 30 cm was prepared using an extrusion molding machine.

(Example 21)

100 parts by weight of a dipolyester polyol using a polyester polyol (70% nonvolatile content, a hydroxyl value of 140, a Dainipton ink Kagaku Kogyo Co., Ltd. product, trade name Banoc DE-140-70) as the liquid A , 3 parts by weight of the antibacterial material of Example 9 (polystyrene) were added.

As B liquid, the prepared diphenylmethane diisocyanate (made by Nippon Polyurethanes Co., Ltd., brand name Milionate MR) was used.

And the antimicrobial paint of this invention which mixed at 100 weight part of A liquids, and 43 weight part of B liquids at the time of use was created.

(Example 22)

The antimicrobial paint of the present invention was mixed with 24 parts by weight of rubber chloride, 8 parts by weight of liquid paraffin, 2 parts by weight of bentonite, 8 parts by weight of bengar, 38 parts by weight of xylol, and 20 parts by weight of the antibacterial material of Example 4 (inorganic particles). Created.

(Example 23)

Antibacterial of Example 4 (Inorganic Particles) to 100 parts by weight of epoxy resin of the water-effect-type two-component epoxy resin (two-component type product name UBE Pregard FG-1400 Mei and Kasei Kabushiki Kaisha, Ltd.) 2 parts by weight of ash was mixed using three rolls, and the antimicrobial paint of the present invention was prepared using a mixture of main agent: effect agent = 1: 1 at the time of use.

(Example 24)

100 parts by weight of the epoxy resin of the water-effect two-component epoxy resin (two-component type trade name UBE Pregard FG-1400 Mei and Kasei Kabushiki Kaisha, Ltd.) Three parts by weight of the antimicrobial material were mixed using three rolls, and an antimicrobial paint of the present invention was prepared using a mixture of main agent: effect agent = 1: 1 at the time of use.

(Example 25)

Example 10 1 part by weight of an antibacterial material of polystyrene was prepared by mixing 10 parts by weight of a commercially available aqueous paint (acrylic synthetic resin, Kanpe Chemical Co., Ltd., trade name aqueous gloss paint (white), product code 627-001). The mixture was added thereto to a commercially available aqueous paint (acrylic synthetic resin, Kanpega Precision Co., Ltd., trade name aqueous gloss paint (white), product code 627-001) to 89 parts by weight, and mixed well, thereby providing an antimicrobial paint of the present invention. Was written.

(Example 26)

20 g of stearic acid, 13 g of calcium stearate, 17 g of glycerin, 1 g of the antimicrobial agent of Example 4 (inorganic particles), 0.5 g of fragrance, and about 50 g of water were kneaded to prepare about 100 g of a varnishing cream.

(Example 27)

60 g of monosodium N-lauroyl glutamate, 10 g of sodium lauryl sulfate, 10 g of N-acetylglycine monostearyl ester, 1 g of the antimicrobial agent of Example 1 (inorganic particles), 8 g of cetyl alcohol, and 12 g of water were kneaded with heat and then pressed. It was molded to obtain a solidifying equipment.

(Example 28)

60 g of monosodium N-lauroyl glutamate, 10 g of sodium lauryl sulfate, 10 g of N-acetylglycine monostearyl ester, 6 g of the antimicrobial agent of Example 11 (polystyrene mixture), 8 g of cetyl alcohol, and 12 g of water were kneaded by heat and then press It was molded to obtain a solidifying equipment.

(Example 29)

A biaxially stretched polypropylene film having an average thickness of 20 µm was obtained in the same manner as in Example 16 except that 1 part by weight of the one of Example 12 was added instead of the antibacterial material of Example 1 as the added antibacterial material.

(Example 30)

20 g of stearic acid, 13 g of calcium stearate, 17 g of glycerin, 1 g of the antimicrobial agent of Example 15 (inorganic particles), 0.5 g of fragrance, and about 50 g of water were kneaded to prepare a varnish cream of about 100 g.

(Example 31)

Titanium oxide fine powder (manufactured by Titanium Kogyo Co., Ltd., product number KR270, average particle diameter of 0.3 µm, specific gravity 4.2) was used as the inorganic particles.

And this inorganic particle is surface-treated and has a positive charge resulting from alumina.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 70 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

Then, an aqueous solution of silver nitrate, in which 28 g of silver nitrate was dissolved in 300 ml of water, was added, left for a while, and then taken out and dried for about 24 ° C. for 24 hours, whereby N-stearoyl-L-glutamic acid silver was attached to the surface of the inorganic particles. About 1 kg of ash (Example 31) was obtained.

(Example 32)

The titanium oxide powder of Example 30 was used as the inorganic particles.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (Ajinomodo Co., Ltd. make, brand name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 52.5 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

Then, silver nitrate, in which 10 g of silver nitrate and 20 g of zinc nitrate were dissolved in 500 ml of water, was added to a mixed solution of zinc chloride, allowed to stand for some time, then taken out and dried at about 70 ° C. for 24 hours. About 1 kg of an antimicrobial agent (Example 32) to which -L-glutamic acid silver and N-stearoyl-L-glutamate was attached was obtained.

(Example 33)

As inorganic particles, fine calcium carbonate powder (manufactured by Nitto Ohkunka Kogyo Co., Ltd., trade name Noverite 3T, average particle diameter of 1 µm, specific gravity of 2.7) was used. And this inorganic particle is surface-treated by the cationic surfactant, and has a positive charge on the surface.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (manufactured by Ajinomodo Co., Ltd., trade name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 70 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

Then, an aqueous solution of silver nitrate, in which 28 g of silver nitrate was dissolved in 300 ml of water, was added, left for a while, and then taken out and dried for about 24 ° C. for 24 hours. About 1 kg of ash (Example 32) was obtained.

(Example 34)

The fine calcium carbonate powder of Example 33 was used as the inorganic particles.

As the alkali metal salt of the N-long-chain acylamino acid, N-stearoyl-L-glutamic acid disodium (manufactured by Ajinomodo Co., Ltd., trade name Amisoft HS-21) was used.

An aqueous N-long-chain acylamino acid solution in which 52.5 g of N-stearoyl-L-glutamic acid disodium was dissolved in 5 L of water was prepared, and 1 kg of inorganic particles was added to the aqueous solution and allowed to stand for some time.

Then, silver nitrate, in which 10 g of silver nitrate and 20 g of zinc nitrate were dissolved in 500 ml of water, was added to a mixed solution of zinc chloride, allowed to stand for some time, then taken out and dried at about 70 ° C. for 24 hours. About 1 kg of anti-bacterial material (Example 34) to which -L-glutamic acid silver and N-stearoyl-L-glutamate was attached was obtained.

(Example 35)

0.5 parts by weight of glycerin monostearate and 1 part by weight of the antimicrobial material prepared in Example 32 were added to 100 parts by weight of polypropylene [melt index (230 ° C.), 2 g / 10 min, density = 0.905 g / cm 2), using a hexyl mixer The mixture was mixed at 80 ° C for 2 minutes, strands were formed at 230 ° C by an extruder having a 40 mm diameter screw, and quenched to obtain strand cut pellets (master pellets, examples). Similarly, 0.5 parts by weight of glycerin monostearate was added to 100 parts by weight of polypropylene [melt index (230 ° C.), 2 g / 10 min, density = 0.905 g / cm 2), followed by mixing at 80 ° C. for 2 minutes using a hesyl mixer. Strands were formed at 230 ° C. with an extruder with a 40 mm diameter screw and quenched to obtain cut pellets.

Then, 10 parts by weight of the master pellets were added to 100 parts by weight of the cut pellets, mixed at 80 ° C for 2 minutes using a Henschel mixer, and a strand was formed at 230 ° C by an extruder having a 40 mm diameter screw. It quenched and obtained strand cut pellet (Example).

This strand cut pellet was inserted into the inflation molding machine, and the polypropylene board of thickness 5mm, long side 150mm, and short side 100mm was created.

[Experiment]

The following experiments were carried out for the above examples.

(Experiment 1) Antibacterial Test

In 500 ml of distilled water, 17.5 g of agar medium (made by Nisui Seiyaku Co., Ltd.) was added, and a medium was prepared. Then, antimicrobial medium 1 to 15 containing about 0.01 g of the antimicrobial material prepared in Examples 1 to 15 were prepared in each of the medium 25g, and a medium in which the antimicrobial material was mixed into the curry was prepared. .1 to No.15).

In addition, the curry No. 16-No. 30 which prepared the thing which added the culture medium which did not mix antimicrobial material to 16 curry separately, and spread about 0.01g of antimicrobial materials of Examples 1-15 on the medium of 15 curry, Share No. 31 which was not scattered was created.

And the said curry of Nos. 1-31 was left to stand outdoors for 24 hours in an open state, and then it put in a heated oven and heated at about 40 degreeC for 24 hours.

And each share was confirmed by the magnification of 10,000 times using the microscope, The growth of a bacterium was not able to be confirmed by Share No.1-No.30 which accommodated the medium which disperse | distributed or mixed antimicrobial material. In addition, significant growth of bacteria was observed in Share No.31.

In addition, 17.5 g of agar medium (made by Nisui Seiyaku Co., Ltd.) and ordinary agar medium was added to 500 ml of distilled water as above, and a medium was prepared. Then, antimicrobial mediums A to D in which about 0.01 g of the antimicrobial material prepared in Examples 31 to 34 were mixed into each of the medium medium 25g were prepared, and a medium into which the antimicrobial material was mixed into the curry was prepared (Shari No. .A to No.D).

And the said No.A-No.D share was left to stand outdoors for about 24 hours in the open state, and then put into the warming oven, and it heated at about 40 degreeC for 24 hours. In addition, when each share was confirmed at a magnification of 10,000 times using a microscope, the growth of bacteria could not be confirmed in all the shares.

(Experiment 2)

The antimicrobial action of the antimicrobial resin molding of the present invention was tested as follows.

As the test strain,

Staphylococcus aureus ATCC 6538P

Klebsiella pneumoniae IFO 13277

Using the same culture medium, the cells were cultured in a buoyon medium at 35 ° C. for 18 to 20 hours to prepare 5.0 × 10 ⁵ to 3.0 × 10 ⁶ cells per ml.

And the test piece which cut each resin molded object of Examples 16-20 and 29 in the size of 20 mm x 20 mm was created, and it sterilized by 121 degreeC and 15 minutes by the autoclave.

In addition, the resin moldings of Examples 16 to 19 and 29 were fixed to prevent shrinkage and sterilized. And 0.2 ml of said bacteria liquid was apply | coated to the surface of the test piece of each Example, and it preserve | saved at 35 degreeC.

After 0 and 18 hours from the start of storage, the live bacteria on the test piece are washed out with sterile buffered saline solution, and the washed solution is mixed with a bacterial counting medium (Agar Chemical Co., Ltd., standard agar medium). ) The viable cell count was measured by plate culture method (35 ° C., 2 days).

The results were as shown in Table 1 and Table 2.

TABLE 1

Table 1 (time-dependent change of viable cell numbers of Staphylococcus aureus)

And-indicates unmeasured.

TABLE 2

Table 2 (time-dependent change of viable cell count of Cleveshella)

And-indicates unmeasured.

(Experiment 3)

The antimicrobial activity of the antimicrobial paint of the present invention was tested.

As the test strains, the followings were used.

Escherichia coli IFO 3301 (E. coli)

Pseudomonas aeruginosa IID P-1 (Pseudomonas aeruginosa)

Staphylococcus aureus IFO 12732

Vivrio parahaemolyticus IFO 12711 (enteritis vibrio)

Aspergillus niger IFO 4407 (Black yeast mold)

In addition, the above bacteria are used as medium bacterium bacteria (E. coli, Pseudomonas aeruginosa, Staphylococcus aureus, AATCC Broth as enteritis vibrio, 3% salt addition AATCC Broth as enteritis vibrio, and Potatodextrose agar as black yeast fungus. [Kaisha Co., Ltd.] was used), the bacteria were incubated at 37 ° C. for 24 hours to prepare a bacterial inoculation solution.

In addition, the black yeast mold was adjusted by floating the biomolecules of the test strain after incubation for 7 days at 25 ° C. in a solution of 0.005% dioctyl sodium sulfosuccinate sodium so that the number of biomolecules per ml was about 108.

In addition, a test medium (E. coli, Pseudomonas aeruginosa, Staphylococcus aureus, AATCC Agar, 3% saline-added AATCC Agar for enteritis vibrio, and 1.5% agar-added GP medium [made by Nissei Seiyaku Kabushiki Kaisha] for black yeast fungus were used). ) Experimental medium in which the inoculating bacterial solution was added at a rate of 1 ml to 150 ml was prepared, dispensed into a sterile shale, and solidified to prepare an experimental flat medium.

Then, a polypropylene sheet having a circular hole with a diameter of 2 cm in the center was placed on a sterile shale filled with the test plate medium so that the circular hole was located approximately in the center of the shale. After spraying about 0.5 ml of a liquid diluted 10 times with water to an antimicrobial paint (aqueous paint), the growth state of the bacteria after incubation at 37 ° C. for 24 hours was confirmed.

As a result, in the share coated with the liquid in which the antimicrobial paint of Example 20 was applied, a portion of about 2 to 2.5 mm of microorganisms was not grown in the center, and the growth of bacteria was observed in other parts of the center. there was.

(Experiment 4)

Test plates coated with the antimicrobial paints of Examples 21, 23, and 24 on a 90 × 180 × 3 mm sandblasted steel sheet coated with a shop primer and an epoxy anti-corrosion primer so as to have a dry film thickness of 100 μm were prepared.

The antimicrobial paints of Example 21 were coated with Liquid A and Liquid B, and the paints of Examples 23 and 24 were mixed within 3 hours after mixing the main ingredient and the effect agent. Each test plate was immersed in seawater for three months in Aichigen Migawa Bay, and the degree of adhesion of aquatic organisms to the test plate was observed.

(Experiment 5)

The antimicrobial activity of the cosmetics of the present invention was tested as follows.

As the experiments, a liquid in which 1 g of the varnishing cream of Examples 26 and 30 was dissolved in 50 ml of water and a liquid in which 1 g of the cosmetic soap of Example 27 was dissolved in 50 ml of water were used.

As the test strains, the followings were used.

Escherichia coli IFO 3301 (E. coli)

Pseudomonas aeruginosa IID P-1 (Pseudomonas aeruginosa)

Staphylococcus aureus IFO 12732

Vivrio parahaemolyticus IFO 12711 (enteritis vibrio)

Then, the above bacteria were incubated at 37 ° C. for 24 hours using enrichment medium bacteria (E. coli, Pseudomonas aeruginosa, Staphylococcus aureus, AATCC Broth as the enteritis vibrio, and 3% saline-added AATCC Broth as the enteritis vibrio), to prepare the inoculum bacteria solution. A test medium was added to the inoculation bacterial medium at a rate of 1 ml to 150 ml of medium (E. coli, Pseudomonas aeruginosa, Staphylococcus aureus, and AATCC Agar for enteritis vibrio). Each of the two flat plate media for each experiment was prepared.

Then, a polypropylene sheet having a circular hole with a diameter of 2 cm in the center was placed on a sterile shale filled with the test plate medium so that the circular hole was located approximately at the center of the shale. And spray coating about 0.5 ml of the liquid in which 30 varnishing creams were dissolved, and spraying approximately 0.5 ml of the liquid in which the makeup soap in Example 27 was dissolved, and then confirming the growth of bacteria after incubating at 37 ° C. for 24 hours. It was.

As a result, in the share which applied the liquid which melt | dissolved the varnish cream of Examples 26 and 30, and the shale which applied the liquid which melt | dissolved the makeup soap of Example 27, the part which does not develop about 2-2.5 mm in the center is observed. In the parts other than the above center, vigorous growth of bacteria was observed.

(Experiment 6)

The antimicrobial action of the antimicrobial resin molding of the present invention was tested as follows.

As the test strain,

Staphylococcus aureus ATCC 6538P

Klebsiella pneumoniae IFO 13277

Using the same medium, bacteria cultured in a buoyant medium at 35 ° C for 18 to 20 hours were prepared using the same medium so that the number of bacteria per mL was 5.0 × 10 ^{5 to} 3.0 × 10 ⁶ .

And the resin molding of Example 35 was sterilized for 15 minutes by 121 degreeC by the autoclave.

And 0.2 ml of said bacteria liquid was apply | coated to the surface of the resin molding, and it preserve | saved at 35 degreeC.

After 0 and 18 hours from the start of preservation, the live bacteria on the test piece are washed out with sterile buffered saline solution, and the washed solution is mixed with a culture medium using a bacterial counting medium (Aesop Kagaku Co., Ltd., standard agar medium). The number of viable cells was measured by 35 degreeC, 2 days).

The results were as shown in Tables 3 and 4.

TABLE 3

Table 3 (time-varying change in viable cell numbers of Staphylococcus aureus)

Table 4 (time-dependent change of viable cell count of Cleveshella)

The first antimicrobial agent of the present invention is an antimicrobial agent in which a metal having an antimicrobial activity is bonded to an N-long chain acylamino acid attached to a surface of an inorganic particle by a hydrophilic organic material.

Since this antimicrobial material is based on inorganic particles, it is easy to control the particle diameter of the formed antimicrobial material, and an antimicrobial material having a particle size according to various uses can be prepared. Inorganic particles can easily prepare the surface of the molecular design and surface modification, high antibacterial activity.

In addition, since the particle diameter and the surface modification can be performed as described above by using the inorganic particles, the formed antimicrobial material can be easily added to resins, fibers, paints and the like.

That is, only N-long-chain acylamino acid antimicrobial metal salt may have insufficient dispersibility, and improves dispersibility.

In addition, the N-acylamino acid antimicrobial metal salt formed on the surface of the antimicrobial material has a very high antimicrobial activity since it is a salt in which at least one antimicrobial metal is bound in each molecule.

In addition, since it is an amino acid that forms the basic skeleton, the toxicity is very low and can be used safely for various purposes.

In addition, in the antimicrobial material of the present invention, since the attached N-long-chain acylamino acid is in a stable state called a water-insoluble salt, only the metal forming the salt is difficult to flow out, which is safe, and a wide range of resin moldings such as foods, films, paper, etc. It can be incorporated in packaging materials.

In addition, the second antimicrobial material of the present invention is an antimicrobial material in which a metal having an antimicrobial activity is bonded to N-long chain acylamino acid attached to the surface of synthetic resin particles or inorganic particles.

In other words, it is an antimicrobial agent to which the N-long-chain acylamino acid salt of the metal which has an antimicrobial effect adhered to the surface of synthetic resin particle. Since this antimicrobial material is based on synthetic resin particles or inorganic particles, the particle size can be easily controlled and the specific gravity can be selected according to the purpose. Thus, the antimicrobial material having a particle size and specific gravity can be used for various applications.

In addition, since the particle size and the specific gravity can be selected by using the synthetic resin particles or the inorganic particles, the formed antimicrobial material can be easily added to resins, fibers, paints and the like.

In addition, an N-acylamino acid antimicrobial metal salt is formed on the surface of the antimicrobial material, and the dimetal salt has high antimicrobial properties and safety as described above.

A method for producing a first antimicrobial material of the present invention comprises the steps of attaching a hydrophilic organic material to the surface of an inorganic particle, a step of contacting a particle having a hydrophilic organic material attached to the surface with an N-long chain acylamino acid ion-containing aqueous solution, After the process, the particles are brought into contact with a metal ion-containing aqueous solution having an antibacterial action.

In addition, the second method for producing an antimicrobial material includes a step of contacting a synthetic resin particle or an inorganic particle with an N-long chain acylamino acid ion-containing solution, and contacting the particle with a metal ion-containing aqueous solution having an antibacterial action after the step. It is a manufacturing method of antibacterial material.

Therefore, it is possible to reliably and easily manufacture the antibacterial material having the above effects.

In addition, in the method for producing the antimicrobial agent, the N-long-chain acylamino acid antimicrobial metal salt, which is insoluble in water formed in advance and is in powder form, is not adhered to the surface of the particles, but is N-long chain on the surface of the particles. Acylamino acid antibacterial metal salt is formed. For this reason, the attachment work is easy.

When the N-long-chain acylamino acid antimicrobial metal salt is formed in advance, the N-long-chain acylamino acid antimicrobial metal salt is agglomerated in the formation process, so that an aggregate of N- long-chain acylamino acid antimicrobial metal salt is also formed in the formed powder.

For this reason, in N-long-chain acylamino acid antimicrobial metal salt powder, it may be in the state which is not exposed to the surface at one part or a substantial part of antimicrobial metal.

In this case, it is anticipated that it cannot fully exhibit the antimicrobial effect.

On the other hand, in the antimicrobial agent prepared by this method, after attaching N-long-chain acylamino acid, it is contacted with an antimicrobial metal ion-containing aqueous solution as a final step, and the N-long-chain acylamino acid antimicrobial metal salt is formed on the surface of the particles. The N-long-chain acylamino acid antimicrobial metal salt is less likely to aggregate, in other words, the N-long-chain acylamino acid antimicrobial metal salt adheres to the surface of the particle in the state of a single molecule or the like, and the antimicrobial metal is exposed. I guess it is.

For this reason, the high antibacterial effect which N-long-chain acylamino acid antimicrobial metal salt has is fully exhibited.

In addition, N-long chain acylamino acids are so-called surfactants and are generally uniformly attached to the surface of the particles.

For this reason, the coating of N-long-chain acylamino acid which is substantially uniform and covers the whole is formed in the surface of particle | grains, and since the metal bonds, the film of N-long-chain acylamino acid antimicrobial metal salt formed also forms the whole surface of a particle | grain. It is generally uniform.

Claims (16)

An antimicrobial material characterized in that a metal having an antimicrobial activity is bonded to an N-long chain acylamino acid attached to a surface of an inorganic particle by a hydrophilic organic substance. An antibacterial material characterized in that a metal having an antimicrobial activity is bonded to an N-long chain acylamino acid attached to the surface of a synthetic resin particle or an inorganic particle. The antimicrobial agent according to claim 1 or 2, wherein the metal is at least one selected from the group consisting of silver, copper, lead, zinc, tin, and bismuth. The antimicrobial material according to any one of claims 1 to 3, wherein the particles have a metal having two or more different antibacterial properties having an antimicrobial effect. N-long-chain acylamino acid salt attached to the surface of the inorganic particles by a hydrophilic organic material, the first antimicrobial inorganic particles in which the first metal having an antimicrobial action is bonded, and on the surface of the inorganic particles by a hydrophilic organic material An antimicrobial material comprising an admixture of a second antimicrobial inorganic particle to which an attached N-long chain acylamino acid salt is bonded to a second metal having a different antimicrobial activity from the first inorganic particle. N-long chain acylamino acid attached to the surface of synthetic resin particles or inorganic particles, to first antimicrobial particles bound to a first metal having an antimicrobial activity, and to N-long chain acylamino acid attached to the surface of synthetic resin particles or inorganic particles. And a mixture of the first antimicrobial particles and the second antimicrobial particles in which a second metal having a different antimicrobial effect is bonded. The antimicrobial agent according to claim 5 or 6, wherein the metal is at least one selected from the group consisting of silver, copper, lead, zinc, tin, and bismuth. The antimicrobial material according to claim 6 or 7, wherein the inorganic particles have a cationic surface. The antimicrobial agent according to any one of claims 1 to 4, wherein the acyl group of the N-long-chain acylamino acid salt is any one of stearoyl group, lauroyl group, myristoyl group, and palmitoyl group. An antimicrobial resin composition comprising the antimicrobial agent of any one of claims 1 to 9. The antimicrobial fiber of any one of Claims 1-9 is contained. The antimicrobial material of any one of Claims 1-9 is contained or adhering to the surface, The paper which has antimicrobial property characterized by the above-mentioned. The antimicrobial paint of any one of Claims 1-9 is contained. Cosmetics characterized by containing the antimicrobial agent of any one of Claims 1-9. Attaching a hydrophilic organic material to the surface of the inorganic particles, contacting the particles with the hydrophilic organic material attached to the surface with an N-long-chain acylamino acid ion-containing aqueous solution, and metal ions having antimicrobial activity after the step. A method for producing an antimicrobial material, characterized by having a step of contacting with an aqueous solution containing. A method for producing an antimicrobial material comprising contacting a synthetic resin particle or an inorganic particle with an N-long-chain acylamino acid ion-containing aqueous solution, and after the step, the particle is contacted with a metal ion-containing aqueous solution having an antimicrobial effect.